Alkylenebisdithiocarbamate complex compounds



United States Patent US. Cl. 260-429 7 Claims ABSTRACT OF THE DISCLOSURENovel complexes of alkanolamiues with zinc-containingethylenebisdithiocarbamates or 1,2-propylenebisdithiocarbamates such ascomplex compounds of from 1 to 4 moles zinc ethylenebisdithiocarbamatewith one mole 2 (2- aminoethylamino)ethanol,(aminoethylethanolamine) areprepared by mixing together a water-soluble ethylenebis-'dithiocarbamate, water-soluble salts of zinc and one or more additionalmetal such as manganese or iron and one or more alkanolamine. Thecomplex compounds are stable and can be used to regulate the growth ofplants. They are useful as antifungal agents for the control of suchfungi as apple scab fungus, rice blast, grape downy mildew and lateblight organisms. They also are useful for promoting the growth ofhigher plants such as grapes, potatoes and the like.

Background of the invention The novel complex compounds of the inventionare stable complexes of zinc-containing ethylenebisdithiocarbamates or1,2-propylenebisdithiocarbamates with alkanolamines. The compounds areuseful as antifungal agents and plant growth regulators.

Many known antifungal agents, when applied to the above-ground portionsof higher plants, give effective fungus control; however, they alsodamage blossoms and young fruit with which they come into contact, andthus cannot be used to equal advantage in all instances. In other cases,antifungal agents which give neither rapid nor complete protection fromfungi have been used because of their low phytotoxicity. Still otherantifungal agents have a low redistribution potential (i.e., poortranslocation characteristics through the plant cellular structure) andmay thus require several days to diffuse outwardly from the immediatezone or area of contact on the plant so as to protect all surfacessubject to fungal attack. During this redistribution time, the activityof the agent decays in substantial measure, with the result thateffective control of the fungus is still not obtained, particularlyunder conditions of severe fungal attack. Still other antifungal agentshave high mammalian toxicity and have thus been hazardous to use in anumber of instances.

It is an object of this invention to provide novel complex compoundswhich are stable, which not only possess the high antifungal activityand good translocation properties, but which also have low phytotoxicitylevels and low mammalian toxicity. It is a further object of theinvention to provide novel complex compounds which possess theabove-described properties and which, in addition, possess the propertyof enhancing the growth of higher plants.

Summary of the invention This invention is directed toalkylenebisdithiocarbamate-alkanolamine complex compounds and to amethod and composition employing the same, and is particularly directedto metallic zinc-containing alkylenebisdithiocarbamate-alkanolaminecomplex compounds wherein the metal is from 30, to 40, to 50, to 60, to70, to 80, to 90, to 95, to 100 mole percent zinc and from 70, to 60,

3,536,742 Patented Oct. 27, 1970 to 50, to 40, to 30, to 20, to 10, to5, to zero mole percent of an additional metal which can be one or moreof manganese, nickel, iron, cobalt or copper; and the alkanolamine isone or more alkanolamine of the formula wherein R represents hydrogen or2-hydroxyethyl and x represents an integer from 1, to 2, to 3, the molarratio of zinc to the alkanolamine in the complex compound being from16:1, to 12:1, to 10:1, to 8:1, to 4:1, to 3:1, to 2:1, to 1:1, to0.521.

The term alkylene is employed in the present specification and claims todesignate ethylene or 1,2-propylene. Thus, the term"alkylenebisdithiocarbamate designates one of ethylenebisdithiocarbamateand 1,2-propylenebisdithiocarbamate.

The term polymetallic zinc-containing alkylenebisdithiocarbamate isemployed in the present specification and claims to designate thepolymeric alkylenebisdithiocarbamate obtained by the reaction of analkylenebisdithiocarbamate ion with an equivalent amount of two or morewater-soluble metal salts, one of which is a zinc salt. In suchcompounds, the metals are chemically combined in amounts correspondingto their starting molar ratios. The zinc and additional metal ions areat least divalent such as manganous, ferrous, cupric, nickelous, ferricand cobaltous ions, and since the alkylenebisdithiocarbamate ion isdivalent, the several ions are combined to form a polymeric product.

Polymetallic zinc-containing alkylenebisdithiocarbamates can also bedescribed as coreacated zinc metal alkylenebisdithiocarbamates inaccordance with the nomenclature of Nemec et al., US. Pat. No.3,210,394.

The invention includes and is exemplified by each com pound wherein themetal is present at any intermediate value between 30 and mole percentof zinc with a corresponding intermediate value for the total quantityof additional metal between 70 and zero mole percent, and wherein theratio of zinc to alkanolamine is present in any intermediate ratio from16:1 to 0.5: 1.

Representative intermediate ratios of zinc to additional metal(zinczadditional metal) include, for example, 31:69, 52.5:47.5,6633:3367, 72.43:27.57 and 99.5:0.5. Representative intermediate molarratios of zinc to alkanolamine (zinczalkanolamine) include such ratiosas 1.3321, 0.721, 2.5:1, 0.93:1, 11:1, 12.8:1 and the like.

For the sake of convenience, the compounds defined above will bereferred to herein simply as complex compounds. Individual complexcompounds will be named as zinc metalethylenebisdithiocarbamate-alkanolamines or zinc metal1,2-propylenebisdithiocarbamate'alkanolamines with the molar percentageof zinc or additional metal being given in parentheses immediatelyfollowing the word zinc or the name of the additional metal, and themolar ratio of zinc to alkanolamine being expressed in parentheses atthe end of the name. In general, the additional metals employed in thecomplex compoundsare employed in a divalent form, with the exception ofiron. When the valence of an additional metal is greater than two, thevalence will be indicated by a Roman numeral following the name of suchmetal, while the absence of a Roman numeral will indicate that the metalis divalent in the complex compound named. E.g., iron is ferrous iron,iron III is ferric iron and copper is cupric copper. When an additionalmetal is present in a hydrated form, as manganese dihydrate, the waterof hydration will be expressed by a term such as dihydrate. In complexcompounds wherein zinc is the sole metal, i.e., the ratio ofzinczadditional metal is 100:9, the molar ratio of zinc to additionalmetal will not be expressed.

The alkanolamine can be from 1, to 2, to 3, to 4, to 5, to 6 of the sixdifferent alkanolamiues represented by the above formula. In general, itis preferred that the alkanolamine be a single specific alkanolamine ora mixture of two specific alkanolamines. In those cases in which thecomplex compound includes more than one type of alkanolamine moiety,each alkanolamine moiety will be expressed separately with the molarratio of the named alkanolamine to Zinc stated parentheticallyimmediately following the name of the alkanolamine, e.g., zincethylenebisdithiocarbamate-diethanolamine(3 1) -2,2'(ethylenediimino)diethanol( 3:1). The alkanolamine moiety can also benamed as an aminoalkanol and such nomenclature is employed herein inlieu of alkanolamine nomenclature in certain cases for the sake ofclarity. In other cases, it is simpler to name the alkanolamine as such.For example, in the present specification and claims, 2-(2-aminoethylamino)ethanol is named aminoethylethanolamine.

Representative complex compounds of the invention, named as describedabove, include zinc ethylenebisdithiocarbamateaminoethylethanolamine 2:1

zinc ethylenebisdithiocarbomate aminoethylethanolamine( 16: 1

zinc 90) iron III manganese dihydrate 5 ethylenebisdithiocarbamateaminoethylethanolamine(3 1 zinc(70 iron( 5 manganese(20) cobalt( 5ethylenebisdithiocarbamate -aminoethylethanolamine( l 1zinc(95)manganese(3 )iron( 2 ethylenebisdithiocarbamate aminoethanol(1 1zinc( 95 copper 5 ethylenebisdithiocarbamate aminoethanol(2:1),

zinc ethylenebisdithiocarbamate aminoethanol (4: 1)

zinc ethylenebisdithiocarbamate 2-( 2-( Z-aminoethylamino) ethyl) -aminoethanol 3 1 1 Zinc ethylenebisdithiocarbamate diethanolamine (2: 1

zinc ethylenebisdithiocarbamate 2,2'-(ethylenediimino diethanol (2 1zinc ethylenebisdithiocarbamate 2,2'- (diethylenetriimino)diethanol(2:1

zinc, l,2-propylenebisdithiocarbamate aminoethylethanolamine( 1.4: 1),

Zinc l,2-propylenebisdithiocarb amate aminoethylethanolamine 3: l),

zinc 1,2-propylenebisdithiocarbamate aminoethylethanolamine( 16: 1),

zinc 1,2-propylenebisdithiocarbamate diethanolamine(3.5:1),

zinc(37.5 )manganese (62.5 1.,2-propylenebisdithiocarbamate-aminoethanol(1 1 zinc(95)manganese( l )iron(l )copper(1)cobalt( l)nickel 1 ethylenebisdithiocarbamate aminoethylethanolamine(2.6:1),

zinc(70)manganese( 30) 1,2-propylenebisdithiocarbamateaminoethylethanolamine (2: 1) -ethanolamine(2: 1

zinc(50) manganese( 50) l,2-propylenebisdithiocarbamateaminoethylethanolamine (l :1),

zinc(90)manganese dihydrate( 5 iron III(5 ethylenebisdithiocarbamateaminoethylethanolamine 3 1 zinc ethylenebisdithiocarbamateaminoethylethanolamine 1 1 zinc ethylenebisdithiocarbamateaminoethylethanolamine 3 1 zinc ethylenebisdithiocarbamateaminoethylethanolamine(12:1),

zinc ethylenebisdithiocarbamate diethanolamine( 3 :1),

zinc ethylenebisdithiocarbamate aminoethanol (0.5 l

zinc (95 manganese 5 ethylenebisdithiocarbamateaminoethylethanolamine(2: l

zinc(70)manganese( 3 0)ethylenebisdithiocarbamate aminoethylethanolamine1.4: 1

zinc( 30 manganese( 70)ethylenebisdithiocarbamateaminoethylethanolamine(3 1 zinc(50)manganese(50)ethylenebisdithiocarbamate aminoethylethanolamine(3 1),zinc()manganese (5 iron III(3 )copper(2)ethylenebisdithiocarb amateaminoethylethanolamine (3 1), zinc ethylenebisdithiocarbamateaminoethylethanoL amine(4: l and zinc ethylenebisdithiocarbamateaminoethylethanolamine 6: 1

The novel compounds of the present invention are generally amorphous orcrystalline solid materials, most of which are white but which may alsohave other colors, particularly when the compound is a polymetalliccomplex compound. The complex compounds are very slightly soluble inwater and organic solvents. The complex compounds form moderately stabledispersions in aqueous solutions of alkanolamines. The complex compoundsevidence characteristic melting or liquefaction points or decompositionpoints. Certain of the complex compounds visibly decompose on heatingwithout appearing to melt or evaporate. On heating, many of the complexcompounds appear to melt or liquefy at a temperature characteristic ofthe particular complex compound; however, cooling of many of the complexcompounds does not always result in resolidification at thecharacteristic melting temperature, nor are the melted and resolidifiedproducts always identical with the original complex compound. The termsmelting and melting point will be employed herein to designate suchcharacteristic temperature at which a particular complex compound melts,liquefies or appears to melt, as distinguished from the temperature atwhich particular complex compounds decompose without melting orevaporating.

The complex compounds of the invention have been found to be useful foraltering the growth of plants. The compounds have been found to inhibitthe growth of lower plants such as fungi, while exhibiting nosignificant phytotoxicity to higher plants. The compounds have also beenfound to enhance the growth of higher plants. The present complexcompounds are particularly useful for the control of a wide range offungi, especially those fungal organisms ordinarily found on the aerialportions or on the seeds of higher plants such as, for example, cherryleaf spot, apple scab, rice blast, downy mildews, damping-off ofcottonseed, Helminthosporium leaf spot on grasses, cereals and corn,cereal rusts, Pythium on corn or pea seeds, Cercospora and Septoria leafspots and late blight. For control of such organisms, a plant or plantpart or plant growth media is contacted with a plant growth-alteringamount of one or more complex compounds of the invention.

The complex compounds of the present invention can be applied to growingvegetation or to seeds of higher plants in amounts required foreffective fungal control without significant injury to the plants. Also,the complex compounds are useful both in eliminating established fungalinfestation as well as in providing residual and extended controlagainst fungal attack. Further, the complex compounds exhibit highredistribution potentials, that is, they are readily distributed ortranslocated through the cellular structure or plant contacted therewithand can thus effect rapid coverage and protection of plant parts whenapplied thereto. Also, application of the present complex compounds tohigher plants in plant growth-altering amounts can beneficially be usedto stimulate plant growth on such crop plants as grapes, potatoes andcelery, for example, even in the absence of significant fungal diseasepressure. It is a yet further advantage that the complex compounds havelow mammalian toxicity and can thus be handled with a minimum of dangerfrom accidental mammalian exposure thereto.

For such uses, preferred complex compounds are those wherein theadditional metal, when present, is trivalent iron or divalent manganese,copper, cobalt or nickel. A preferred group of complex compoundsincludes those wherein the mole ratio of Zinc to additional metal isfrom 60:40 to :0 and wherein the additional metal is divalent manganese,copper, cobalt or nickel or ferric iron. A preferred group of compoundsincludes those complex compounds wherein the mole ratio of the zinc tothe additional metal is from 60:40 to :0, the additional metal isselected from manganese and iron, the alkanolamine is one wherein R ishydrogen and the molar ratio of zinc to alganolamine is from 1:1 to 8:1.Another preferred group of compounds includes those wherein thealkanolamine is aminoethylethanolamine. Another preferred group ofcompounds includes those wherein the mole ratio of zinc to theadditional metal is from about 90:10 to 100:0, wherein the additionalmetal is manganese or iron or both, wherein the alkanolamine isaminoethylethanolamine and wherein the mole ratio of zinc toalkanolamine is from 1:1 to 4: 1.

The complex compounds of the invention can be prepared by the reactionof a water-soluble alkali metal or ammonium alkylenebisdithiocarbamate,water soluble salts of zinc or mixtures of water-soluble salts of zincand additional metals and an alkanolamine corresponding to the aboveformula. Representative water-soluble alkylenebisdithiocarbamatestarting materials include ethylenebisdithiocarbamate or1,2-propylenebisdithiocarbamate salts of lithium, sodium, potassium orammonium, for example. Representative water-soluble salts of zinc ormanganese, iron, copper, nickel or cobalt include the chloride, sulfate,nitrate or acetate salts, for example. The alkanolamine reactant ispreferably added as the free base, though salts thereof such as thesulfates, phosphates, nitrates, hydrohalides, acetates, citrates and thelike can also be employed. When the alkanolamine is employed as a salt,the acidity of the reaction mixture is adjusted by the addition of abase such as sodium hydroxide to liberate the free base alkanolamine.

The complex compounds are formed when the reactants are contacted andmixed in an inert solvent. Representative inert solvents which can beemployed as reaction media include water, methanol, ethanol, isopropanoland mixtures thereof, aqueous media being preferred. The reactionproceeds at temperatures between about 10 and 50 C. in an aqueous oralcoholic medium and is generally complete in from about 2 to 60minutes. The zinc-containing alkylenebisdithiocarbamate alkanolaminecomplex compound product precipitates in the reaction mixture. Theprecipitated product can be isolated by filtration, decautation,centrifugation or other conventional methods and the product can bepurified by conventional proceudres such as washing with water,methanol, aqueous methanol or the like to remove any unreacted startingmaterials which may be present. The complex compound product can beemployed to control fungi and enhance plant growth directly with orWithout purification, or it can be purified by washing and dried underambient or reduced pressures at temperatures which are well below thedecomposition point of the particular product. Temperatures of fromabout 35 to 75 C. are advantageously employed in drying the product.

The reactants combine to form a zinc-containingalkylenebisdithiocarbamate complex compound when mixed together in anyproportions; however, the identity of the product produced in a giveninstance is dependent upon the molar proportions of certain of thereactants employed.

Thus, in the preparation of the polymetallic complex compounds of theinvention, it is critical and essential that the water-soluble salts ofthe zinc and the additional metal or metals be employed in substantiallythe same molar proportions (based on the metal content of each salt) asare desired to be obtained in the final product. The water-soluble zincor additional metal salt reactants are thus employed in such proportionsas to provide zinc ions in the reaction mixture in the amount of fromabout 30 to 100 mole percent of the metal ions provided by suchreactant. When substantially less than 30 mole percent of the metal ionsare provided by the zinc salt, such as 10 or 20 mole percent, theproduct obtained will contain a corresponding ratio of zinc to theadditional metal and will not possess many of the desirable plantgrowthaltering properties of the complex compounds of the invention. Therelative proportions of water-soluble alkylenebisthiocarbamate andwater-soluble zinc or additional metal salts are not critical and anyunreacted excess of either reactant can be separated from the complexcompound product by conventional procedures such as filtration andwashing. In a preferred procedure, the water-soluble salts of zinc orthe additional metals and the water-soluble alkylenebisdithiocarbamateare employed in stoichiometric proportions. Thus, it is preferred toemploy sufficient alkylenebisdithiocarbamate to react with the zinc andmetal reactants without employing a significant excess ofalkylenebisdithiocarbamate.

The minimum amount of alkanolamine reactant to be employed is likewisecritical to the preparation of the complex compounds. Sufficientalkanolamine must be employed to provide at least one-sixteenth molarproportion of alkanolamine for eacry molar proportion of zinc in thedesired product. When substantially less alkanolamine is employed, suchas 0.02 or 0.01 molar proportion of alkanolamine per molar proportion ofzinc, products are obtained which contain little or no alkanolamine andwhich lack many desirable plant growth-altering properties, such as highantifungal potency. When using one or more additional metal saltreactants along with zinc, the molar content of the zinc alone is takeninto account when calculating the amount of alkanolamine. In such acase, the alkanolamine reactant is employed in an amount of at leastone-sixteenth the molar proportion of zinc salt reactant employed. Whenthe alkanolamine reactant is a mixture of two or more alkanolamines, thetotal molar quantity of alkanolamine reactants must be at leastone-sixteenth the molar quantity of zinc to be present in the desiredproduct. It is generally preferred to employ all the reactants instoichiometric amounts, in which case from one-sixteenth to 2 molarproportions of alkanolamine reactant are employed for every molarproportion of zinc salt reactant. In most cases, the exact proportionsof zinc salt reactant and alkanolamine to be employed correspond to themolar ratio of zinc and alkanolamine desired in the final product. Whenthe final product is to contain from 1 to 2 moles of alkanolamine permole of zinc, or when the alkanolamine reactant contains secondaryamino, but no primary amino group, the use of an excess of alkanolaminereactant is preferred.

Under a given set of reaction conditions of temperature, solvent, moleconcentrations of reactants and the like, a greater or lesser excess ofalkanolamine may be required to produce a complex compound having aparticular molar ratio of zinc to alkanolamine. In any such case,elemental analysis of the solid complex compound will readily provideinformation as to the molar ratio of zinc to alkanolamine in the productobtained. When the product is found by elemental analysis to contain ahigher or lower ratio of zinc to alkanolamine than desired, the excessof alkanolamine reactant employed can be increased or decreased,respectively, to produce a product having the desired ratio. Simple androutine variations in the amount of alkanolamine reactant will enableone to determine the exact excess of alkanolamine to be employed underany given set of reaction conditions to obtain a product having aparticular ratio of zinc to alkanolamine.

In a convenient procedure for the preparation of the complex compoundsof the invention, a water-soluble alkylenebisdithiocarbamate, awater-soluble zinc salt, an

alkanolamine corresponding to the above formula and,

optionally, one or more additional metal salts are mixed together withan inert solvent, preferably water, in any order or fashion. In apreferred procedure, the water-soluble alkylenebisdithiocarbamate isfirst dissolved in the inert solvent and the alkanolamine reactant,water soluble zinc salt and additional water-soluble metal salts areadded 7 to the solution in the required proportions. The amount of inertsolvent employed is preferably such as to provide from about to about 25percent by weight of solids in the ultimate reaction mixture. In suchprocedure, the alkanolamine reactant, the water-soluble zinc salt andany additional metal salt employed can be mixed together in the requiredproportions with additional inert solvent and added as a solution, orthey can be added individually to the alkylenebisdithiocarbamatesolution. When it bamate solution, it is preferred to mix the manganesesalt prior to adding the mixture to the alkylenebisdithiocarbamatesolution, it is prefrred to mix the manganese salt and alkanolamine inmethanol. The reaction mixture is then mechanically mixed and held at atemperature within the reaction temperature range until precipitation ofthe complex compound is complete. The product is conveniently separatedfrom the reaction mixture by filtration. The complex compound isobtained as a filter cake which can be employed directly to alter thegrowth of plants, including fungal plants. Alternatively, the productcan be washed with water or methanol and dried by conventionalprocedures. When a complex compound containing manganese is not dried,or is dried at temperatures less than about 40 C., the complex compoundproduct generally contains the manganese in the form of the dihydrate.Drying the product at temperatures of 70 C. or higher removes the waterof hydration. Complex compounds containing either the hydrated ordehydrated manganese are similarly useful for influencing the growth ofplants. Since the hydrated manganese complex compounds require noparticular isolation or drying steps for their preparation, they aregenerally more convenientlv employed in plant growth-influencingoperations,

In an alternate method of preparation, the complex compounds can beprepared by the reaction of one or more alkanolamines corresponding tothe above formula with a zinc alkylenebisdithiocarbamate or with apolymetallic zinc-containing alkylenebisdithiocarbamate. These salts canbe employed either per se or in the form of a wettable powdercomposition containing surfactants or the like in which the salts arepresent. The formation of the complex compound proceeds when thereactants are mixed together in an inert aqueous or alcoholic liquidreaction medium, preferably water. The reaction proceeds at temperaturesfrom about to about 50 C. and is generally complete in from about 30 toabout 120 minutes. The complex compound product can be employed directlyto influence the growth of plants by the application of the diluted orundiluted reaction mixture to plants or plant parts. Alternately, theproduct can be separated and purified by conventional procedures such asfiltration and washmg.

The proportions of the reactants to be employed generally correspond tothe molar ratio of zinc to alkanolamine to be obtained in the product.Consequently, it is essential that at least one-sixteenth molarproportion of alkanolamine be employed for each molar proportion of zincin the zinc-containing alkylenebisdithiocarbamate starting material. Theuse of substantially less alkanolamine reactant, such as onethirty-second or one sixtyfourth mole per mole of zinc, results in aloss of desirable plant growth-altering properties such as antifungalpotency and lack of phytotoxicity, and in the preparation of productscontaining little or no alkanolamine. If the complex compound is tocontain a precise amount of the alkanolamine such as, for example, A1,/2 or mole of alkanolamine per mole of zinc, then the alkanolamine andthe zinc-containing reactant should be employed in correspondingproportions. In such operations, the mixture is well stirred and is heldfor a sufiicient period of time for the reaction to go to completion.

When it is desired to prepare a complex compound which contains morethan about one mole of the alkanolamine per mole of zinc, or when thealkanolamine reactant is one which contains secondary but no primaryamine groups, or when the composition is to be employed immediatelyafter the reactants are mixed to control fungi or promote the growth ofhigher plants, then the preferred practice is to add excess alkanolaminein amounts of from about 3 to 10 moles of alkanolamine per mole of zinc,the relatively larger excesses acting in many cases to dissolve ordisperse the zinc-containing alkylenebisdithiocarbamate in the reactionmedium. The complex compound which thereafter forms in the mixture or isprecipitated therefrom will contain from 1 to 2 moles of alkanolamineper mole of zinc in most cases. Elemental analysis of the purifiedproduct can be employed to determine the ratio of zinc to alkanolamineobtained in any particular case. The excess of alkanolamine to beemployed under particular reaction conditions can be increased ordecreased depending upon whether the zinc:alkanolamine ratio in theproduct is higher or lower than the exact ratio desired. Routinevariations in the excess alkanolamine employed will enable one to obtaina complex compound product having a particular ratio of zinc toalkanolamine.

In a convenient procedure, a zinc-containing alkylenebisdithiocarbamate,an alkanolamine and inert solvent, preferably water, are mixed togetherin any order or fashion. The reaction mixture is held at a temperaturewithin the reaction temperature range for a period of time sufficientfor the reaction to go to completion, with mixing being continued tomaintain the zinc-containing alkylenebisdithiocarbamate in suspension.The reaction mixture containing the product can be employed directly inantifungal and plant growth regulatory operations, or the product can beseparated by filtration and purified by washing with water or methanol.

Description of the preferred embodiments The following examples areillustrative of the invention but are not to be construed as limiting.

EXAMPLE 1 Disodium ethylenebisdithiocarbamate hexahydrate (218.4 grams;0.6 mole) is dissolived in 3 liters of water and the solution is mixedthoroughly with aminoethylethanolamine (62.4 grams; 0.6 mole). Thesolution is stirred while a solution of zinc chloride (81.77 grams; 0.6mole) in milliliters of water is added gradually thereto over a periodof about ten minutes. A white precipitate forms in the reaction mixtureduring the addition of the zinc chloride. The reaction mixture isstirred for an additional thirty minutes after which the mixture isfiltered. The filter cake is washed twice with water and once withmethanol. The washed product is oven-dried overnight at a temperature of40 C. The zinc ethylenebisdithiocarbamate-aminoethylethanolamine(1:1)product is obtained as a white, finely divided amorphous solid which isfound to be substantially insoluble in water, alcohols and other organicsolvents. The product has a melting point of about 133135 C. Elementalanalysis is consistent with the assigned structure. The product is foundby elemental analysis to have carbon, hydrogen, nitrogen and sulfurcontents of 25.11, 4.59, 14.98 and 33.56 percent, respectively, ascompared with theoretical values of 25.36, 4.74, 14.76 and 33.74percent, respectively, calculated for the complex compound zincethylenebisdithiocarbamateaminoethylethanolamine (1 1).

The above procedure is repeated with the sole variations beingsubstitution of aminoethylethanolamine dihydrochloride for theaminoethylethanolamine and the addition of suflicient sodium hydroxideto adjust the pH of the mixture to about 7 immediately prior to theaddition of the Zinc chloride. The zincethylenebisdithiocarbamate-aminoethylethanolamine( 1:1) product isobtained as a white finely divided solid which appears to melt onheating at about 133-134 C. The structure of the product is confirmed byelemental analysis.

The above procedure is repeated employing 0.65 mole of disodiumethylenebisdithiocarbamate hexahydrate, 0.325 mole ofaminoethylethanolamine and 0.65 mole of zinc chloride. The zoncethylenebisdithiocarbamate-aminoethylethanolamine(2:1) product isobtained as a white finely divided solid which is substantiallyinsoluble in water and organic solvents and which melts on heating at143-146 C. Elemental analysis of the product discloses the complexcompound to have carbon, hydrogen, nitrogen, sulfur and zinc contents of21.58, 3.58, 13.03, 38.52 and 20.1 percent, respectively, as compared tothe theoretical values of 21.99, 3.67, 12.83, 39.1 and 19.97 percent,respectively, calculated for the named structure.

The above procedure is again repeated employing 0.28 mole of disodium1,2-propylenebisdithiocarbamate, 0.20 mole of aminoethylethanolamine and0.028 mole of zinc chloride. A zinc1,2-propylenebisdithiocarbamate-aminoethylethanolamine(1.4:1) product isobtained as a white finely divided amorphous solid which issubstantially insoluble in water and organic solvents and whichdecomposes on heating at about 129 C. Elemental analysis of the productdiscloses the complex compound to have carbon, hydrogen, nitrogen andsulfur contents of 25.4, 4.4, 13.2 and 35.2 percent, respectively, ascompared to the theoretical values of 25.84, 4.53, 13.14 and 35.34percent, respectively, calculated for the named structure.

EXAMPLE 2 An aqueous suspension of Zinc ethylenebisdithiocarbamate isprepared by slowly adding a solution of zinc chloride (88.59 grams; 0.65mole) in 125 milliliters of water to a solution of disodiumethylenebisdithiocarbamate hexahydrate (236.6 grams; 0.65 mole) in 3liters of water with vigorous stirring. The addition is carried out overa period of about six minutes. To the resulting stirred suspension isthen slowly added, over a period of about five minutes, a solution ofaminoethylethanolamine (33.8 grams; 0.325 mole) in 100 milliliters ofwater. The reaction mixture is then stirred for 30 minutes after whichthe solid present therein is filtered off and washed, first with waterand then with methanol. All operations are conducted under ambientconditions. The washed solid is dried overnight at a temperature of 40C. yielding 200 grams of an insoluble, finely divided, white amorphoussolid. The structure of the zincethylenebisdithiocarbamate-aminoethylethanolamine(2:1) product isconfirmed by elemental analysis.

In the remainder of the present specification, the following conventionwill be employed to express elemental analysis data. The elementsassayed will be listed, each element being named by a conventionalabbreviation, followed by the percentage of each named element found andlastly, by the percentage calculated to be present in the named product.In each list of found or calculated percentage values, the order inwhich the values are set out corresponds to the order in which theelements were named. For example, in the case of zinc1,2-propylenebisdithiocarbamate-aminoethylethanolamine( 1 6:1), theexpression C, H, N, S, Zn; found; 21.2, 2.9, 10.1, 43.2, 22.1;calculated: 21.3, 3.0, 10.1, 43.3, 22.1 percent means that the namedcompound is found by elemental analysis to have carbon, hydrogen,nitrogen, sulfur and zinc contents of 21.2, 2.9, 10.1, 43.2 and 22.1percent, respectively, as compared with the theoretical contents of21.3, 3.0, 10.1, 43.3, and 22.1 percent, respectively, calculated forthe named structure.

EXAMPLE 3 A solution of 0.02 mole of zinc chloride and 0.12 mole ofaminoethylethanolamine in 10 milliliters of water is mixed with asolution of 0.02 mole of disodium ethylenebisdithiocarbamate hexahydratein about 10 milliliters of water. A white crystalline solid precipitatesslowly in the reaction mixture. The mixture is held at ambienttemperature and pressure for about 3 to 4 hours. The filter cake iswashed with water and filtered and dried overnight in a 40 C. oven. Thedried zinc ethylenebisdithio- 10 carbamate-aminoethylethanolamine(0.5:1) product is found to melt at 123 -125 C. Elemental analysis confirmsthe composition of the product. C, H, N, S, Zn; found: 30.1, 6.1, 18.0,27.7, 13.1; calculated: 29.8, 6.2, 17.4, 26.5, 13.5 percent. The productis substantially insoluble in water but forms stable dispersions inaqueous aminoethylethanolamine.

In substantially the same procedures as those employed above and inExamples 1 and 2, disodium ethylenebisdithiocarbamate, zinc chloride andaminoethylethanolamine are reacted together to prepare the followingcomplex compounds, which are characterized by melting temperatures andby elemental analysis.

Zinc ethylenebisdithiocarbamate-aminoethylethanolamine(3:1), melting at163166 C.; C, H, N, S, Zn; found: 20.3, 3.3, 12.0, 41.2, 21.1 percent;calculated: 20.6, 3.2, 12.0, 41.3, 21.1 percent.

Zinc ethylenebisdithiocarbamate aminoethylethanolamine(4:1), melting at174-177 C.; C, H, N, S, Zn; found: 19.7, 2.9, 11.5, 42.1, 21.7 percent;calculated: 19.9, 3.0, 11.6, 42.5, 21.7 percent.

Zinc ethylenebisdithiocarbamate aminoethylethanolamine(6:1), melting at180-184 C.; H, S, Zn; found: 2.6, 43.6, 22.1 percent; calculated: 2.7,43.7, 22.3 percent.

Zinc ethylenebisdithiocarbamate-aminoethylethanolamine(8:'l), melting at188-190 C., C, H, Zn; found: 18.7, 2.6, 22.4 percent; calculated: 18.4,2. 6, 22.7 percent.

Zinc ethylenebisdithiocarbamate aminoethylethanolamine(12:1), melting at193-1 96 C.; N, H, Zn; found: 10.7, 2.6, 22.6 percent; calculated: 10.7,2.5, 23.0 percent.

Zinc ethylenebisdithiocarbamate-aminoethylethanolamine(16:1), melting at198201 C.; C, N, Zn; found: 17.9, 10.7, 22.9 percent; calculated: 18.1,10.6, 23.1 percent.

EXAMPLE 4 0.02 mole of disodium ethylenebisdithiocarbamate hexahydrateand 0.019 mole of aminoethylethanolamine are dissolved in 100milliliters of water. A solution of 0.019 mole zinc chloride and 0.001mole of manganese chloride in 3 milliliters of water is added to theresulting solution with vigorous stirring. After the addition iscomplete, the mixture is stirred for 30 minutes at ambient temperatures.The mixture is filtered and the filter cake is carefully washed withwater and dried overnight in a 40 C. oven. The zinc(95)manganesedihydrate(5)ethylenebisdithiocarba-mate-aminoethylethanolamine( 1:1)product is obtained as a white amorphous powder which melts at C. Thecomposition of the product is confirmed by elemental analysis. C, H, S,Zn, Mn; found: 25.1, 4.7, 34.2, 16.6, 0.7; calculated: 25.0, 4.7, 34.1,16.5, 0.7 percent.

In substantially the same procedure, the following complex compounds areprepared.

Zinc( 95 )manganese dihydrate( 5)ethylenebisdithiocarbamate-aminoethylethanolamine(2:1) is prepared asan insoluble light purple colored amorphous powder, melting at 153156C., by the reaction of 0.02 mole of disodiumethylenebisdithiocarbornate, 0.019 mole zinc chloride, 0.001 molemanganese chloride and 0.0095 mole aminoethylethanolamine. C, H, N;found: 21.6, 3.8, 12.7; calculated: 21.7, 3.7, 12.7 percent.

Zinc 95 )manganese dihydrate( 5)ethylenebisdithiocarbamate-aminoethylethanolamine(3:1) is prepared asan insoluble purple amorphous powder, melting at 158 16l C., by thereaction of 0.020 mole of disodium ethylenebisdithiocarbamate, 0.019mole zinc chloride, 0.001 mole manganese chloride and 0.0063 moleaminoethylethanolamine in aqueous solution. C, H; found: 20.5, 3.0;calculated: 20.4, 3.2 percent.

Zinc (95 )manganese dihydrate 5)ethylenebisdithiocarbamate-aminoethylethanolamine(4:1) is prepared asan insoluble purple amorphous powder, melting at 164- 167 C., by thereaction of 0.020 mole disodium ethylenebisdithiocarbamate, 0.019 molezinc chloride, 0.001 mole 1 1 manganese chloride and 0.0048 moleaminoethylethanolamine in aqueous solution.

Zinc( 95 manganese dihydrate()ethylenebisdithiocarbamate-aminoethylethanolamine(8:1) is prepared asan insoluble faint purple amorphous powder, melting at 164 167 C., bythe reaction of 0.020 mole disodium ethylenebisdithiocarbamate, 0.001mole manganese chloride, 0.019 mole zinc chloride and 0.0024 moleaminoethylethanolamine in aqueous solution.

Zinc( 95 manganese dihydrate( 5)ethylenebisdithiocarbamate-2-aminoethanol(2: 1) is prepared as anamorphous insoluble powder containing 19.6 percent carbon, 11.3 percentnitrogen and 20.3 percent zinc by the reaction of 0.020 mole disodiumethylenebisdithiocarbamate with 0.019 mole zinc chloride, 0.001 molemanganese chloride and 0.0095 mole Z-aminoethanol in aqueous solution.

Zinc( 95 )copper( 5 )ethylenebisdithiocarbamateaminoethylethanolamine(1:1) is obtained as a tan insoluble powder,melting at 129132 C., by the reaction of 0.019 mole each of zincchloride and aminoethylethanolamine, 0.001 mole of cupric chloride and0.020 mole of disodium ethylenebisdithiocarbamate. H, N, S; found: 4.5,14.5, 33.9; calculated: 4.7, 14.6, 34.2 percent.

Zinc(95)manganese dihydrate(5)1,2propylenebisdithiocarbamate-aminoethylethanolamine(8:1) is prepared asan insoluble finely divided amorphous solid having nitrogen and zinccontents of 10.3 and 20.5 percent by the reaction of 0.020 mole disodium1,2-propylenebisdithiocarbamate, 0.001 mole manganese chloride, 0.019mole zinc chloride and 0.0024 mole aminoethylethanolamine in aqueoussolution.

Zinc(95 )iron(5 1,2 propylenebisdithiocarbamate 2- aminoethanol(2: 1) isprepared as an amorphous insoluble powder containing 10.9 percentnitrogen and 19.6 percent zinc by the reaction of 0.020 mole disodiumethylenebisdithiocarbamate with 0.019 mole zinc chloride, 0.001 moleferrous chloride and 0.0095 mole 2-aminoethanol in aqueous solution.

EXAMPLE 5 A solution of 0.16 mole of aminoethylethanolamine and 0.02mole zinc chloride in 50 milliliters of methanol is added dropwise to asolution of 0.02 mole of disodium ethylenebisdithiocarbamate hexahydratein 75 milliliters of methanol with vigorous stirring. A whiteprecipitate forms immediately upon the addition. The resulting mixtureis then stirred for an additional thirty minutes after which it isfiltered. The filter cake is washed with methanol and dried overnight ina 40 C. oven. The zincethylenebisdithiocarbamate-aminoethylethanolamine(0.5 :1) product isobtained as a White, amorphous, finely divided solid which issubstantially insoluble in water and organic solvents and which can betaken up in aqueous aminoethylethanolamine. The product is found to meltat 123 125 C. Elemental analysis confirms the structure of the product.C, H, N, S; found: 29.9, 6.0, 17.7, 27.1; calculated: 29.8, 6.2, 17.4,26.5 percent.

In substantially the same procedure, the following complex compounds areprepared.

Zinc ethylenebisdithiocarbamate diethauolamine(2: 1) is obtained as acream-colored insoluble powder, melting at 114l16 C., by employingdiethanolamine in lieu of the aminoethylethanolamine in the aboveprocedure. C, H, N; found: 21.7, 3.6, 10.5; calculated: 21.9, 3.5, 10.7percent.

Zinc ethylenebisdithiocarbamate 2,2 (ethylenediimino)diethanol(2:1) isobtained as a cream-colored insoluble powder, melting at 117123 C., byemploying 2,2- (ethylenediimino)diethanol in lieu ofaminoethylethanolamine in the above procedure.

Zinc(95 cobalt(5 ethylenebisdithiocarbamate aminoethylethanolamine(3:1)is obtained as a lime green insoluble powder, melting at 164l66 C., byemploying 0.019 mole of zinc chloride, 0.007 mole ofaminoethylethanolamine and 0.001 mole of cobalt chloride in the aboveprocedure.

12 Zinc 5 0 cobalt 50) ethylenebisdithiocarbamateaminoethylethanolamine(1:l) is obtained as a green insoluble powder,which decomposes without melting at 185l89 C., by employing 0.01 moleeach of zinc chloride and aminoethylethanolamine and 0.01 mole of cobaltchloride in the above procedure.

EXAMPLE 6 0.4 mole of disodium ethylenebisdithiocarbamate hexahydrateand 0.36 mole of aminoethylethanolamine are dissolved in 2 liters ofwater. To this solution is slowly added, with vigorous stirring, asolution of 0.36 mole zinc chloride, 0.012 mole ferricchloride, 0.008mole cupric chloride and 0.02 mole of manganese chloride in millilitersof water. After this addition is complete, the mixture is stirred atroom temperature for about 0.5 hour. A solid precipitate forms duringthe mixing and stirring. The mixture is filtered and the filter cake isWashed with water and dried overnight in a 40 C. oven. The zinc(90)ironIII 3 copper 2 manganese dihydrate 5 ethylenebisdithimcarbamate-aminoethylethanolamine(1:1) product is obtained as abeige-colored, insoluble, amorphous powder which melts at 124-127 C. Thecomposition of the product is confirmed by elemental analysis. C, H, N;found: 24.4, 4.4, 14.4; calculated: 24.7, 4.6, 14.4 percent.

The above procedure is repeated Without substantial variation other thanthe designated changes in the named reactants to prepare the followingcomplex compounds. The structure of each product is confirmed byelemental analysis.

Zinc(90)manganese dihydrate(5)iron III(3)copper(2)-ethylenebisdithiocarbamate-aminoethylethanolamine(3:1 is obtained as alight gray insoluble powder, melting at 154-160 C., by employing 0.12mole of aminoethylethanolamine in the above procedure. C, H; found:20.1, 3.2; calculated: 20.3, 3.2 percent.

Zinc(90 manganese dihydrate (5 ironIII(5)ethylenebisdithiocarbamate-aminoethylethanolamine(4:1) is obtainedas a charcoal gray-colored insoluble powder, melting at 158161 C., byemploying 0.09 mole of aminoethylethanolamine and 0.020 mole of ferricchloride and omitting the cupric chloride in the above procedure.

Zinc iron III 30 ethylenebisdithiocarb amate aminoethylethanolamine(1 1)is obtained as a charcoal graycolored insoluble powder, melting at138l42 C., by employing 0.28 mole each of zinc chloride andaminoethylethanolamine and 0.12 mole of ferric chloride and omitting thecupric chloride and manganese chloride in the above procedure.

Zinc()manganese dihydrate(5)iron III (5)ethylenebisdithiocarbamate-aminoethylethanolarnine(3:1) is obtained asa brown insoluble powder, which decomposes when heated to a temperatureof 148152 C., by employing 0.12 mole of aminoethylethanolamine and 0.02mole of ferric chloride and omitting the cupric chloride in the aboveprocedure.

Zinc nickel (5) ethylenebisdithiocarbamate-aminoethylethanolamine(1:1)is obtained as a light green insoluble powder, melting at 129 C., byemploying 0.38 mole each of zinc chloride and aminoethylethanolamine and0.020 mole of nickel chloride and omitting the manganese, ferric andcupric chlorides in the above procedure.

- C, H, N, S; found: 25.0, 4.6, 14.9, 34.5; calculated: 25.0,

4.6, 14.6, 34.2 percent.

Zinc (95 iron III(5 ethylenebisdithiocarbamateaminoethylethanolamine(1:1) is obtained as a brown insoluble powder,melting at 128l31 C., by employing 0.38 mole each of zinc chloride andaminoethylethanolamine and 0.02 mole of ferric chloride and omitting theman- (ganese chloride and cupric chloride in the above proceure.

Zinc (30) manganese (70) ethylenebisdithiocarbamate'aminoethylethanolamine( 16:1) is obtained as an insoluble amorphouspowder containing 16.9 percent carbon, 44.3 percent sulfur and 6.8percent zinc by employing 0.12 mole of zinc chloride, 0.0075 mole ofaminoethylethanolamine and 0.28 mole of manganese chloride and omittingthe ferric and cupric chlorides in the above procedure, and drying theproduct at 70 C.

Zinc (95) copper (5)1,2-propylenebisdithiocarbamateaminoethylethanolamine(1:1) containing27.2 percent carbon, 33 percent sulfur and 16 percent zinc is obtainedas an amorphous insoluble powder by the reaction of 0.019 mole each ofzinc chloride and aminoethylethanolamine, 0.001 mole of cupric chlorideand 0.020 mole of disodium 1,2-propylenebisdithiocarbamate and omittingthe ethylenebisdithiocarbamate salt and the manganese and ferricchlorides in the above procedure.

Zinc (70) nickel(3 ethylenebisdithiocarbamate aminoethy1ethanolamine(1:1) is obtained as a green insoluble powder, melting at 124127 C., byemploying 0.28 mole each of zinc chloride and aminoethylethanolamine and0.12 mole of nickel chloride and omitting the manganese, ferric andcupric chlorides in the above procedure. H, N; found: 4.11, 13.73;calculated: 4.16, 13.75 percent.

Zinc (95 cobalt III(5 ethylenebisdithiocarbamateaminoethylethanolamine(3:1) is obtained as a green insoluble powdercontaining 20.5 percent carbon, 12 percent nitrogen and 20.2 percentzinc by employing 0.38 mole of zinc chloride, 0.127 mole ofaminoethylethanolamine and 0.02 mole of cobaltic chloride and omittingthe manganese chloride and cupric chloride in the above procedure.

EXAMPLE 7 0.6 mole of disodium ethylenebisdithiocarbamate hexahydrate isdissolved in 3 liters of water and the resulting solution is mixed withstirring with 0.2 mole of aminoethylethanolamine and 0.2 mole ofethanolamine. A solution of 0.6 mole zinc chloride in 125 milliliters ofwater is added to the mixture with stirring over a ten minute period.After this addition is complete, the mixture is stirred for about 0.5hour. The mixture is filtered and the filter cake is washed with waterand dried overnight at a temperature of 40 C. The zincethylenebisdithiocarbamate aminoethylethanolamine (3:1) ethanolamine (3:1) product is obtained as a white insoluble amorphous powder whichmelts at 140-144 C. The composition of the product is confirmed byelemental analysis. C, H, Zn; found: 21.6, 3.6, 19.9; calculated: 21.8,3.7, 19.8 percent.

The above procedure is repeated without substantial variation other thanthe designated changes in the amounts of the named reactants to preparethe following complex compounds. The structure of each product isconfirmed by elemental analysis.

Zinc ethylenebisdithiocarbamate-ethanolamine(8:1) is obtained as a whiteinsoluble powder, melting at 200- 203 C., by employing 0.075 mole ofethanolamine and omitting the aminoethylethanolamine in the aboveprocedure.

Zinc ethylenebisdithiocarbamate-2 [2(2-aminoethylamino)ethyl]aminoethanol(12:-1) is obtained as a whiteinsoluble powder, melting at 178 181 C., by employing 0.05 mole of 2 [2(2-aminoethylamino)ethyl]-aminoethanol in lieu of theaminoethylethanolamine and aminoethanol in the above procedure. C, H, N;found: 18.7, 2.6, 10.7; calculated: 18.8, 2.6, 11.0 percent.

Zinc ethylenebisdithiocarbamate-2,2' (diethylenetriimino)diethanol(2:1)is obtained as a white insoluble powder by employing 0.30 mole of2,2-(diethylenetriimino)diethanol in lieu of the aminoethylethanolamineand aminoethanol and ethanol in lieu of water in the above procedure.

Zinc ethylenebisdithiocarbamate-2-[2(Z-aminoethylamino)ethyl]aminoethanol(6:1) is obtained as a whiteinsoluble powder,-melting at -171174 C., by employing 0.1 mole of2-[2-(2-aminoethylamino)ethyl]aminoetha- I101 in lieu of theaminoethylethanolamine and aminoethanol in the above procedure.

Zinc ethylenebisdithiocarbamate-2-[2-(2aminoethylamino)ethyl]aminoethanol(3:1) is obtained as a white insolublepowder, melting at 156 -15 8 C., by employing 0.2 mole of2-[2-(2-aminoethylamino)ethyl] aminoethanol in lieu of theaminoethylethanolamine and aminoethanol in the above procedure. H, N,Zn; found: 3.6, 12.4, 19.87; calculated: 3.6, 12.95, 20.15 percent.

Zinc ethylenebisdithiocarbamate-ethanolamine(1: 1) is obtained as awhite insoluble powder, melting at 140- 142 C., by employing 0.60 moleof ethanolamine and omitting the aminoethylethanolamine in the aboveprocedure. C, H, Zn; found: 21.2, 3.7, 19.4; calculated: 21.4, 3.9;'19.4 percent.

Zinc ethylenebisdithiocarbamate-ethanolamine(4:1) is obtained as a whiteinsoluble powder, melting at 198- 202 C., by employing 0.15 mole ofethanolamine and omitting the aminoethylethanolamine in the aboveprocedure. C, N, Zn; found: 18.3, 10.6, 22.6; calculated: 18.6, 10.8;22.5 percent.

EXAMPLE 8 0.4 mole of disodium ethylenebisdithiocarbamate hexahydrateand 0.36 mole of aminoethylethanolamine are dissolved in 2 liters ofwater. To this solution is slowly added, with vigorous stirring, asolution of 0.36 mole zinc chloride and 0.04 mole of mangenese chloridein 60 milliliters of Water. Ambient conditions are used. After thisaddition is complete, the mixture is stirred for about 0.5 hour duringwhich time a solid precipitate forms. The mixture is filtered and thefilter cake is washed with water and dried overnight in a 40 C. oven.The zinc(90)manganese dihydrate (10)ethylenebisdithiocarbamate-aminoethylethanolamine(1:l) product isobtained as a light brown insoluble amorphous powder which melts at 129C. The composition of the product is confirmed by elemental analysis. C,H; found: 24.4, 4.6; calculated: 24.55, 4.63 percent.

The above procedure is repeated without substantial variation other thanthe designated changes in the amounts of the named reactants to preparethe following complex compounds. The structure of each product isconfirmed by elemental analysis.

Zinc()manganesedihydrate(20)ethylenebisdithiocarbamate-aminoethylethanolamine(l:1) isobtained as a light brown insoluble powder, melting at l42l44 C., byemploying 0.32 mole each of zinc chloride and aminoethylethanolamine and0.08 mole of mangenese chloride.

Zinc 80 manganese dihydrate 20)ethylenebisdithiocarbamate-aminoethylethanolamine(1.6:1) is obtained asa light tan insoluble powder, melting at 144-146 C., by employing 0.32mole of zinc chloride, 0.20 mole of aminoethylethanolamine and 0.80 moleof manganese chloride.

Zinc(70)manganesedihydrate(30)ethylenebisdithiocarbamate-aminoethylethanolamine(.l:1) isobtained as a light brown insoluble powder, melting at 141 144 C., byemploying 0.28 mole each of zinc chloride and aminoethylethanolamine and0.12 mole of manganese chloride.

Zinc 60) manganese dihydrate (40ethylenebisdithiocarbamate-aminoethylethanolamine(1:1) is obtained as abrown insoluble solid, melting at 137-140 C, by employing 0.24 mole eachof zinc chloride and aminoethylethanolamine and 0.16 mole of manganesechloride.

Zinc 50) manganese dihydrate (50ethylenebisdithiocarbamate-aminoethylethanolamine(3 1) is obtained as apurple-brown insoluble powder, melting at 153 155 C., by employing 0.20mole of zinc chloride, 0.067 mole of aminoethylethanolamine and 0.20mole of manganese chloride.

Zinc (3 0) manganese dihydrate 7 0)ethylenebisdithiocarbamate-aminoethylethanolamine(3:1) is obtained as abrown insoluble powder, melting at 158161 C. by employing 0.12 mole ofzinc chloride, 0.04 mole of aminoethylethanolamine and 0.28 mole ofmanganese chloride. H, N, Zn; found: 3.3, 10.0, 42.6; calculated: 3.3,10.1, 42.2 percent.

The complex compounds of the invention can be used to alter the growthof plants including both fungal plants and the higher plants. When thecomplex compounds are employed to control fungus attack, the complexcompounds are employed by contacting fungi and their habitats with aplant growth-altering amount which is also an antifungal amount of oneor more of the complex compounds, the term habitat herebeing used in itsbroadest sense to include higher plants and plant parts thereof, growthmedia and any other spaces, areas or surfaces with which fungi may comeinto contact. The term higher plant includes the chlorophyllous plantshaving leaves, stems, roots and the like such as the angiospermae andgymnospermae. When the complex compounds are employed as plant growthstimulants, they are employed by containing portions of higher plantsincluding plant parts such as the leaves, stems, seeds, flowers orfruits thereof with a plant growth-altering amount which is also agrowth-stimulating amount of one or more of the compounds. In general,when the compounds are employed to control fungal attack on higherplants or plant parts, an antifungal amount is also a growthstimulatingamounts to the higher plant, so that contacting higher plants with anantifungal amount of a complex compound also provides stimulation andimprovement of the growth of the higher plant.

In such operations, the complex compounds are advantageously employed tocontrol fungal attack or stimulate growth or both on such representativehigher plants as almond, apple, apricot, banana, cherry, peach, pear,grape, carrot, tomato, cabbage, cucumber, cantaloupe, spinach, potato,beet, corn, hops, rice, wheat, beans, cotton, lettuce, onions, celery,tobacco and other crop plants as well as ornamental shrubs and floweringplants and turf grasses. In such operations, the higher plant or plantpart is contacted with a plant growth-altering amount of a complexcompound of the invention. Such plant growth-altering amount is at leastan antifungal amount or a growth-stimulating amount, depending on theeffects or combination of effects to be produced. It is essential thatsuch antifungal or growth-stimulating amount be less than a phytotoxicamount, that is, the amount of complex compound which deleteriouslyaffects the growth of the higher plant by injuring the higher plant orplant parts, substantially inhibiting the growth, flowering orreproduction thereof or the like. For example, when applied to groWingplants, application at rates in excess of about pounds of complexcompound per acre is generally unnecessary to obtain good antifungal andgrowth-stimulating results, and can produce phytotoxic responses andinhibition of the growth of many higher plants. Excellent control offungi and stimulation of the growth of higher plants is observed whenthe complex compounds are applied to the above-ground portions of higherplants in amounts from about 0.004 to about 3 pounds of complex compoundper acre or when aerial portions of higher plants are contacted withcompositions containing from about 25 to about 2400 or more parts byweight of complex compound per million parts by weight of totalcomposition. Similarly, application of complex compounds to seeds ofhigher plants in amounts of from about 0.5 ounce to about 16 ounces ofcomplex compound per 100 pounds of seed provides excellent control offungi without inhibiting germination of the seed and growth of plantstherefrom.

When it is desired to control fungi and effects on higher plants can bedisregarded as when wood, storage bins, paper, cloth and the like are tobe treated, or when fungal control is to be obtained in fungal growthmedia other than the aerial portions of higher plants such as in thetreatment of soil or orchard floors, the complex com pounds are employedin a plant growth-altering amount which is an antifungal amount. In suchoperations, the compositions are applied at rates of from about 0.004 toabout 3, to about pounds per acre or in amounts sufiicient to providethe complex compound in the fungal habitat in concentrations of at least1 part by weight of complex compound per million parts by weight offungal habitat or substrate. For application to soil, it is usuallyunecessary to apply more than about 100 pounds of complex compound peracre of soil, and in most cases, excellent antifungal results can beobtained at application rates of from about 0.004 to about 50 pounds peracre. In other operations, the complex compounds are applied to fungi ortheir growth media or habitats, wrapping papers, storage bins and thelike as compositions containing at least about one part or more byweight of complex compound per million parts by weight of growth mediaor habitat such as soil, wood, paper or the like.

The complex compounds can be employed in their unmodified form or theycan be employed in compositions comprising additaments and adjuvants,preferably a nonphytotoxic adjuvant. The term non-phytotoxic adjuvantrefers to conventional fungicide adjuvants which are not substantiallydeleterious to plant leaves, stems, flowers, fruit and the like and notsubstantially inhibitory to the growth of plants at rates of applicationof complex compounds consistent with good plant growth-alteringactivity. Such compositions can contain from about 0.0001 or less toabout 2 percent or more by Weight of a complex compound. Liquidcompositions can include one or more fungicide adjuvant such as aqueousalkanolamines, alcohols, acetone, toluene, petroleum distillates,dimethylsulfoxide and the like. Dust compositions can be formulated byemploying finely divided solid adjuvant such as powdered Walnut shells,pyrophyllite, chalk, talc, gypsum or the like and can include solidsurface active dispersing agents such as fullers earth, bentonite,kieselguhr, attapulgite clay and the like. The compositions can also beprepared as concentrate compositions containing from about 2 to about 98percent of a complex compound. Such compositions are adapted to bediluted by admixture with additional adjuvants prior to use.

The complex compounds can also be incorporated with other active agentsto provide combinations of effects or synergistic results in particularoperations. For example, the compositions can include additionalfungicides or preservatives such as the phenolic preservatives,halogenated salicylanilides, sulfur, copper fungicides and the like;insecticides, nematocides, fumigants and other pesticides such asdichlorodiphenyltrichloroethane, hexachlorocyclohexane, malathion,diethyl-p-nitrophenylrnonothiophosphate, methyl bromide, ethylenedibromide, 0,0- diethyl O-(3,5,6-trichloro-2-pyridyl)-phosphoroLhioate,4- dimethylamino-3,5-xylyl methyl-carbamate and the like; fertilizersincluding ammonium, phosphate and urea fertilizers and trace mineralplant nutrients; and pre-emergent or post-emergent herbicides such asthe halogenated phenoxy aliphatic acids, dinitro-secondary-butylphenol,3- (3,4-dichlorophenyl)-l,l-dimethylurea and the like. When the complexcompounds are employed to treat higher plants, any other active agentsare selected to provide a composition which will provide the desiredadditional effects such as control of insects, slugs, nematodes andweeds without adversely affecting the plant species treated.

The compositions can also be formulated as wettable powders includingionic or non-ionic surface active dispersing agents. A preferred groupof compositions in cludes those comprising a complex compound and asurface active dispersing agent. The term surface active dispersingagent is employed herein to include all agents which are capable ofacting as the interfacial surface between the complex compounds andwater or an organic liquid as the dispersion medium, facilitatingthereby the dispersion of the complex compound in water or organicliquid to form dispersible concentrate compositions or the like.Representative surface active dispersing agents include bentonite,fullers earth, attapulgite and other clays, condensation products ofalkylene oxides with phenols and organic acids, alkyl aryl sulfonates,fatty acid esters of sugars and ethylene oxide derivatives thereof,polyoxylethylene derivatives of sorbitan esters, complex alcohols,mahogany soaps and the like. Other suitable surface active dispersingagents can be found in Detergents and Emulsifiers, Up to Date'writtenand published by John W. McCutcheon, Inc., Morristown, N.J., 1967. Thepreferred compositions comprising a complex compound and a surfaceactive dispersing agent can be treating compositions containing fromabout 0.0001 or less to about 2 or more percent by weight of the complexcompound, or they can be concentrate compositions containing from about2, to 40, to 50, to 90, to 98 percent by weight of a complex compound.The concentrate compositions can be diluted by the addition of water,organic solvents, additaments, non-phytotoxic adjuvants and the like toprepare the ultimate treating compositions.

Another preferred group of compositions includes those comprising acomplex compound and a dispersion stabilizer. The term dispersionstabilizer is employed herein to include those agents which act topromote the dispersion of the complex compounds in aqueous or organicliquid systems and to inhibit the settling of solids therefrom, andwhich generally act to increase the viscosity of the liquid dispersionmedium. Such dispersion stabilizers also contribute to the holding ofthe active complex compounds on plant parts or the like when thecompositions are employed as sprays. Representative dispersionstabilizers which can be employed include alginic acid, blood albumin,carboxymethyl cellulose, casein, gluten, starch, linear and/ orcross-linked polyacrylamides, natural and artificial gums such as gumarabic, guar gum, hydroxypropylmethyl cellulose and hydroxypropylcellulose, pectins, gelatin and the like and compatible mixturesthereof. Compositions comprising a complex compound and from about 0.25to about 20 to about 95 percent of a dispersion stabilizer provideexcellent plant growth-altering results in liquid dispersions. Suchcompositions provide deposits of increased amounts of complex compoundson plant parts when applied as sprays at given application rates. Spraycompositions containing a complex compound and from about 0.25 to about20 percent by weight of a dispersion stabilizer selected from the loweralkyl and hydroxy lower alkyl cellulose ethers wherein lower alkyl ismethyl, ethyl or propyl are particularly preferred, andhydroxypropylmethyl cellulose is a dispersion stabilizer of choice.

The complex compounds and compositions containing In a representativeoperation, excellent control of late blight organism, Phytophthorainfestans, is obtained when tomato plants are treated with an aqueuoscomposition containing one of zinc ethylenebisdithiocarbamateaminoethylethanolamine( 1 l zincethylenebisdithiocarbamateaminoethylethanolamine 8 1 zincethylenebisdithiocarbamate aminoethylethanolamine l6 1 zincethylenebisdithiocarbamate 2- [2-(2-aminoethylamino) ethyl]aminoethanol(2 1 zinc1,2-propylenebisdithiocarbamate-aminoethylethanolamine( 1.4: 1),

zinc ethylenebisdithiocarbamate-ethanolamine(2:1) or zinc manganesedihydrate 5 ethylenebisdithiocarbamate ethanolamine (0.5: 1)

as the sole active agent therein and at a concentration of 1200 parts byweight of complex compound per million parts by weight of composition.In such operations, the compositions are applied as sprays to theabove-ground portions of tomato plants and the plants are thereafterinoculated with a suspension of viable spores of Phytophthora infestans(late blight). Similar plants not thus treated with a complex compoundare similarly inoculated to serve as checks. All the plants are held forfour days under conditions of temperature and high humidity conducive tothe growth of the fungal organism. Observations of the plants treatedwith a complex compound of the invention show excellent control offungal attack and prevention of late blight infestation, the treatedplants being healthy and growing vigorously, while the untreated checkplants show heavy fungal infestation with attendant injury to theplants.

In a similar representative operation, excellent controls of Plasmophoraviticola are obtained when the aboveground portions of grape plants aretreated with aqueous spray compositions containing one of zinc (95copper(5 ethylenebisdithiocarbamate aminoethylethanolamine( 1 1 zinc(60) manganese dihydrate (40) ethylenebisdithiocarbamateaminoethylethanolamine 1 1 zinc (95 )nickel (5ethylenebisdithiocarbamate aminoethanolamine 1: 1),

zinc(90) manganese dihydrate (5 iron IH(5 )ethylenebisdithiocarbamateaminoethylethanolamine (4: 1 or zinc ethylenebisdithiocarb amateethanolamine (3 l aminoethylethanolamine (3 l as the sole activeingredient therein at a concentrationof 600 parts per million, and theplants are thereafter inoculated with viable spores of Plasmophoraviticola, the downy mildew organism. The treated plants are observed tobe in a state of vigorous healthy growth throughout the test period.

In other representative operations, aqueous suspensions containing 600parts per million of one of zinc ethylenebisdithiocarbamateaminoethylethanolamine (1:1) or zinc1,2-propylenebisdithiocarbamate-aminoethylethanolamine( 1:1) are appliedto portions of the leaves of young bean plants. The suspensions areapplied in uniform droplets of 50 microliters each and allowed to dryovernight. The bean plants are then inoculated over the entire leafsurface with viable spores of bean rust (Uromyces phase0li)'and held forone week under conditions conductive to 'the growth of bean rust.Similar untreated plants are similarly inoculated and held to serve aschecks. At the end of the test period, the check plants show widespreaderuption of bean rust pustules over the entire inoculated leaf surface.Observations of the treated plants show pustule-free zones of leafsurface surrounding each portion'treated with a complex compound andextending about 2 centimeters beyond such treated portions. Such resultsindicate redistribution and translocation of the complex compoundthrough the plant structure without significant loss of antifungalactivity. In other representative operations, mature healthy grapeplants of the Carignane variety are sprayed three times through thegrape blooming period at approximately one week intervals 'with an'aqueous suspension containing one pound of zincethylenebisdithiocarbamate-aminoethylethanolamine(1:1) per gallons, thespray being applied at a plant growth-altering amount of approximately100 gallons per acre. Similar grape plants are left untreated to serveas checks. No injury to any of the plants is detected and at the end ofthe growing season, the yield and quality of the fruit is determined.The check plants are found to produce about 12.2 pounds of grapes pervine, about 22.5 percent of such grapes being #1 market grade. Theplants treated with zincethylenebisdithiocarbamate-aminoethylethanolamine(1:1) are found toproduce about 21.7 pounds of grapes per vine, with about 44 percent ofsuch grapes being #1 grade.

The alkanolamine starting materials employed to prepare the complexcompounds of the invention can be prepared in conventional procedures bythe reaction of ethylene oxide with excess ammonia or with an excessalkylamino or hydroxyalkylamino compound. The reaction is carried out bymixing the ethylene oxide with excess ammonia, alkylamine orhydroxyalkylamine in a lower alcohol at a reaction medium. The reactionproceeds readily at ambient temperatures and pressures, and the desiredalkanolamine product can be obtained by conventional techniques such asby stripping off the reaction medium and any unreacted startingmaterials. For example, aminoethylethanolamine can be prepared by addingethylene oxide to an excess of ethylenediamine. Diethanolamine isprepared by adding ethylene oxide to an excess of Z-aminoethanoldissolved in ethanol. The reaction proceeds rapidly under ambientconditions, and the desired product is recovered from the crude reactionmixture by fractional distillation under reduced pressure.

The water-soluble alkylenebisdithiocarbamate starting materials can beprepared by known methods such as those described in US. Pat. Nos.2,317,765, 2,609,389 and 2,844,623. In a representative method, thesoluble alkylenebisdithiocarbamates of such metals as sodium, lithium orpotassium or of ammonium are prepared by the reaction of carbondisulfide with ethylenediamine or 1,2-propylenediamine and a base whichcan be an alkali metal hydroxide or ammonium hydroxide. The reaction iscarried out in an inert solvent for the ethylenediamine or1,2-propylenediamine such as methanol, ethanol, isopropanol or water andproceeds at temperatures of from about 25 to 50 C. Thealyklenebisdithiocarbamate product is obtained as a solution in theinert solvent. The solution of product can be employed directly in thepreparation of the complex compounds of the invention, or it can bereduced in volume by evaporation or distillation to remove all or partof the solvent.

The zinc alkylenebisdithiocarbamate starting materials employed toprepare the complex compounds can be prepared by conventional methods.In a representative procedure, the salt can be formed by the metatheticreaction of a water-soluble zinc salt with a water-solublealkylenebisdithiocarbamate. The reaction is carried out in an aqueoussolvent as a reaction medium and the insoluble zincalkylenebisdithiocarbamate is obtained as a precipitate. Alternatively,the insoluble zinc alkylenebisdithiocarbamate can be prepared by mixingcarbon disulfide with an aqueous solution of ethylenediamine and awatersoluble zinc salt. The zinc alkylenebisdithiocarbamate product isobtained as a precipitate.

The polymetallic zinc-containing alkylenebisdithiocarbamate startingmaterials are members of a known class of polymeric compounds which canbe described as coreacted alkylenebisdithiocarbamates in accordance withNemec et al., US. Pat. No. 3,210,394. They can be prepared in methodsanalogous to those of Nemec et al. by the metathetic reaction of awater-soluble alkylenebisdithiocarbamate salt such as an alkali metal orammonium salt with a mixture of water-soluble salts of zinc and theadditional metal or metals such as the chlorides, sulfates, acetates orthe like. The zinc and additional metal salts are employed in the molarratio which is desired in the polymetallic product. The reaction isconveniently carried out in water as a reaction medium. The productprecipitates from the reaction mixture and can be purified byconventional techniques such as washing.

The polymetallic zinc-containing alkylenebisdithiocarbamate materialscan be characterized and distinguished from mixtures of metallic saltsby their physical properties in procedures such as those described byNemec et al. and including elemental analysis, X-ray diifraction andspectroscopic analysis.

The polymetallic zinc-containing alkylenebisdithiocarbamate startingmaterials can also be prepared by the reaction of ethylenediamine or1,2-propylenediamine, carbon disulfide and a mixture of soluble salts ofzinc and the additional metal or metals. Such procedure is analogous tothat employed for the preparation of zinc alkylenebisdithiocarbamates.

What is claimed is:

1. A metallic zinc-containing alkylenebisdithiocarbamate-alkanolaminecomplex compound wherein the metal is from 30 to 100 mole percent zincand from to zero mole percent of an additional metal selected from thegroup consisting of manganese, nickel, iron, cobalt and copper; thealkanolamine corresponds to one or more alkanolamines of the formula inwhich R represents a member of the group consisting of hydrogen andZ-hydroxyethyl and x represents one of the integers two or three; andthe molar ratio of zinc to the alkanolamine is from 16:1 to 0.5 :1,inclusive.

2. The compound of claim 1 wherein the additional metal is selected fromthe group consisting of manganese and iron.

3. The compound of claim 1 wherein the alkanolamine isaminoethylethanolamine.

4. The compound of claim 1 wherein the compound is a zinc-containingethylenebisdithiocarbamate-alkanolamine complex compound.

5. The compound of claim 4 wherein the additional metal is selected fromthe group consisting of manganese and iron, the molar ratio of zinc tothe alkanolamine is from about 8:1 to about 1:1, inclusive, and themetal is from about 70 to mole percent zinc.

6. The compound of claim 5 wherein the alkanolamine isaminoethylethanolamine.

7. The compound of claim 6 wherein the ratio of zinc to theaminoethylethanolamine is from 1:1 to 4:1, inclusive.

References Cited UNITED STATES PATENTS 3,082,229 3/ 1963 Nash 260429FOREIGN PATENTS 7,043 11/ 1967 South Africa. 6716267 6/ 1968Netherlands. 1,042,569 11/1958 Germany.

HELEN M. MCCARTHY, Primary Examiner A. P. DEMERS, Assistant Examiner US.Cl. X.R.

25353 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,536,72 Dated 27 October 1970 lnventofl Robert L. Noveroske It iscertified that error appears in the above-ideritified patent and thatsaid Letters Patent are hereby corrected as shown beluw:

In column 7, line 10, delete "bamate solution. it is preferred to mixthe" and insert is desired to mix the alkanolanflne with a Signed andsealed this 13th day of April 1971.

[SEAL] Attest: EDWARD M.FLET( 3HER,J'R. WILLIAM E. SCHUYLER, JR. Attestng Officer Commissioner of Patents

